Insecticidal tricyclic derivatives

ABSTRACT

It has now been found that certain tricyclic derivatives have provided unexpected insecticidal activity. These compounds are represented by formula I: wherein R 1  through R 8 , inclusively, and X and Y are fully described. Compositions comprising an insecticidally effective amount of at least one compound of formula I, and optionally, an effective amount of at least one of a second compound, with at least one insecticidally compatible carrier are also disclosed; along with methods of controlling insects comprising applying said compositions to the locus where insects are present or are expected to be present.

FIELD OF THE INVENTION

The present invention generally relates to insecticidal compounds andtheir use in controlling insects. In particular, it pertains toinsecticidal tricyclic derivatives and agriculturally acceptable saltsthereof, compositions of these insecticides, and methods for their usein controlling insects.

BACKGROUND OF THE INVENTION

It is well known that insects can cause significant damage to cropsgrown in agriculture, resulting in loss of millions of dollars of valueassociated with a given crop. Although there are many orders of insectsthat can cause significant crop damage, insects of the suborder“Homoptera” are of major importance. The suborder Homoptera includes,for example, aphids, leafhoppers, cicadas, whiteflies, and mealybugs, toname a few. Homopterans have piercing/sucking mouthparts, enabling themto feed by withdrawing sap from vascular plants. Insect damage fromhomopterans is manifested in several different ways, other than damagecaused by direct feeding. For example, many species excrete honeydew, asticky waste product that adheres to plants upon which the insect feedsand lives. Honeydew alone causes cosmetic injury to crop plants. Sootymolds will often grow on honeydew, making food products or ornamentalplants look unappealing, thereby reducing their cosmetic and economicvalue. Some homopterans have toxic saliva that is injected into plantswhile they are feeding. The saliva can cause plant damage throughdisfigurement and in some instances plant death. Homopterans can alsovector disease-causing pathogens. Unlike direct damage, it does not takea large number of disease-vectoring insects to cause considerable damageto crop plants.

Accordingly, there is a continuing demand for new-insecticides forcontrol of, for example, Homoptera and other orders of insects; as wellas new acaricides, that are safer, more effective, and less costly foruse on crops such as wheat, corn, soybeans, potatoes, and cotton to namea few. For crop protection, insecticides and acaricides are desiredwhich can control the insects and acarids without damaging the crops,and have no deleterious effects to mammals and other living organisms.

Its equivalent WO93/00811 and U.S. Pat. No. 5,366,975 disclose a methodof controlling an invertebrate pest, comprising contacting the pest witha pest-controlling amount of an agent having substantial inhibitoryactivity toward a phenylethanolamine reuptake transporter as determinedby a radioactive octopamine reuptake inhibition assay. Compounds incompositions capable of inhibiting the octopamine transporter set forthin WO93/00811 and U.S. Pat. No. 5,366,975 include tricyclicantidepressants, wherein the tricyclic antidepressants exemplified aredesipramine, amitriptyline, imipramine, amoxapine, nortriptyline,protriptyline, maprotiline, and doxepin, and pharmaceutically acceptablesalts thereof. Desipramine and amitriptyline are specifically shown tohave anti-feeding activity against tobacco hornworm. The tricyclicantipruritic cyproheptadine is also disclosed as having anti-feedingactivity against tobacco hornworm.

The disclosure of invertebrate pesticidal activity of certain tricyclicantidepressants and antipruritics in WO93/00811 and U.S. Pat. No.5,366,975, based on the limited data presented therein, does not suggestinsecticidal activity, or the degree of that insecticidal activity, ofother tricyclic derivatives whose antidepressant or antipruriticactivity is unknown.

U.S. Pat. No. 3,436,397 claims a class of dibenzocyclohepten-5-ylidenethiazolidinones of the formula:

wherein R is selected from the group which consists of hydrogen andC₁-C₄ alkyl. The dibenzocyclohepten-5-ylidene thiazolidinones arereported to have larvicidal activity against horse strongyles,anthelminthic activity against Syphacia obvelata and are useful for thetreatment of pinworm infestations in mammals, and also possessantibacterial activity against certain gram-positive and gram-negativeorganisms.

There is no disclosure or suggestion in U.S. Pat. No. 3,436,397 that anyof the compounds disclosed therein have insecticidal activity.

SUMMARY OF THE INVENTION

In accordance with the present invention, it has now been found thatcertain tricyclic derivatives (hereinafter termed “compounds of formulaI”) and agriculturally acceptable salts thereof are surprisingly activewhen used in the insecticidal compositions and methods of thisinvention. The compounds of formula I are represented by the followinggeneral formula I:

wherein

-   R¹ through R⁸, inclusively, are independently selected from    hydrogen, halogen, alkyl, cycloalkyl, alkenyl, alkynyl,    trialkylsilylalkynyl, alkoxy, haloalkyl, haloalkoxy, alkylthio,    alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl,    haloalkylsulfonyl, dialkylaminosulfonyl, nitro, cyano, amino,    formyl, or alkylcarbonyl;-   X is selected from —CR⁹R¹⁰—, —CR¹¹R¹²CR¹³R¹⁴—, —CR¹⁵═CR¹⁶—, NR¹⁷—,    —CR¹⁸R¹⁹NR²⁰—, or —CR²¹═N—;    and-   Y is selected from —CR²²R²³, —CR²⁴R—CR²⁶R²⁷—, CR²═CR²⁹—, —NR³⁰—,    —CR³¹R³²NR³³—, —O—, —S—, —S(O)—, —S(O)₂—, —CR³⁴R³⁵O—, —CR³⁶R³⁷S—, or    —CR³⁸═N—;    where-   R⁹ and R¹⁰ are independently selected from hydrogen, alkyl, or    (piperidin-4-yl)alkyl;    or-   R⁹ and R¹⁰ may be taken together with    or with ═CHC₂H₄NR⁴⁰R⁴¹,    where-   R³⁹, R⁴⁰ and R⁴¹ are independently selected from hydrogen; alkyl;    hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl, wherein aryl is optionally substituted with    one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁴⁰ and R⁴¹ may be taken together with —C₂H₄N(CH₃)C₂H₄— to form a    piperazine ring;-   u is 0 or 1,-   and when u is 1, an N-oxide is formed;-   n is 0, and R^(a) is hydrogen;    or-   n is 1 to 8, and R^(a) is selected from one or more of alkyl,    alkoxyalkyl, alkoxycarbonyl, and aryl, wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R¹¹ is selected from hydrogen, alkyl, alkylaminoalkoxy,    dialkylaminoalkoxy, N(alkyl)(alkylaminoalkyl),    N(alkyl)(dialkylaminoalkyl), alkylaminoalkylalkynyl,    dialkylaminoalkylalkynyl, morpholinyl, imidazolinyl,    alkylpyrrolidinyloxy,    where    v is 0 or 1,    and when v is 1, A is a bridging group selected from —O—, —S—, —NH—,    and —CH₂—;    u is as described above;-   R⁴² through R⁴⁵, inclusively, are independently selected from    hydrogen; alkyl; alkenyl; alkynyl; hydroxylalkyl; alkoxyalkyl;    alkylthioalkyl; alkylcarbonyl; alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl; heteroaryl; heteroarylalkyl;    heteroarylalkylamino; wherein aryl and heteroaryl are optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁴³ and R⁴⁴ may be taken together with —C₅H₁₀— to form a piperidine    ring; m, p, and q are 0, and R^(b), R^(c) and R^(d) are hydrogen;    or-   m is 1 to 8, p is 1 to 7, and q is 1 to 10, and R^(b), R^(c), and    R^(d), respectively, are independently selected from one or more of    alkyl, alkoxyalkyl, alkylamino, dialkylamino, alkoxycarbonyl, or    aryl, wherein aryl is optionally substituted with one or more    halogen, alkoxy, haloalkyl, or aryl;    or-   R¹¹ and R¹² may be taken together with    where R^(a), n, u, and R³⁹ are as described above;-   R¹², when not taken together with R¹¹, and R¹³, R¹⁴, and R¹⁶, are    independently selected from hydrogen, hydroxy, halogen, alkyl,    alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,    alkoxycarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl,    alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylaminosulfonyl,    or dialkylaminosulfonyl;-   R¹⁵ is selected from    where m, u, v, A, R^(b) and R⁴² are as described above;-   R¹⁷ is hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or —C₃H₆NR⁴⁷R⁴⁸    where-   A, v, and u are as described above;-   R⁴⁶ is selected from selected from hydrogen; alkyl; alkenyl;    alkynyl; hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl;    alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;    arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl;    heteroarylalkyl; heteroarylalkylamino; wherein aryl and heteroaryl    are optionally substituted with one or more halogen, alkoxy,    haloalkyl, or aryl;-   R⁴⁷ and R⁴⁸ are independently selected from hydrogen and alkyl;    or-   R⁴⁷ and R⁴⁸ may be taken together with —C₅H₁₀— to form a piperidine    ring, or with —C₂H₄N(CH₃)C₂H₄—, or —C₂H₄N(C₂H₄₀H)C₂H₄— to form a    piperazine ring;-   R¹⁸ and R¹⁹ are independently selected from hydrogen, alkyl, amino,    alkylaminoalkyl, and dialkylaminoalkyl;-   R²⁰ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R²¹ is selected from hydrogen, alkyl,    where-   A, v, and u are as described above;-   R⁴⁹ through R⁵², inclusively, are independently selected from    hydrogen; alkyl; alkenyl, alkynyl, hydroxylalkyl; alkoxyalkyl;    alkylthioalkyl; alkylcarbonyl, alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl, heteroaryl, heteroarylalkyl,    heteroarylalkylamino, wherein aryl and heteroaryl are optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁵⁰ and R⁵¹ may be taken together with —C₅H₁₀— to form a piperidine    ring;-   r, s, and t are 0, and R^(e), R^(f), and R^(g) are hydrogen,    or-   r is 1 to 8, s is 1 to 7, t is 1 to 10, and R^(e), R^(f), and R^(g),    respectively, are independently selected from one or more of alkyl,    alkoxyalkyl, alkylamino, dialkylamino, alkoxycarbonyl, or aryl,    wherein aryl is optionally substituted with one or more halogen,    alkoxy, haloalkyl, or aryl;-   R²² through R²⁹, inclusively, are independently selected from    hydrogen, and alkyl;-   R³⁰ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R³¹ and R³² are independently selected from hydrogen, and alkyl,-   R³³ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R³⁴ through R³⁸, inclusively, are independently selected from    hydrogen, and alkyl;    and,    agriculturally acceptable salts thereof.

The present invention is also directed to compositions containing aninsecticidally effective amount of at least one of a compound of formulaI, and optionally, an effective amount of at least one of a secondcompound, with at least one insecticidally compatible carrier.

The present invention is also directed to methods of controllinginsects, where control is desired, which comprise applying aninsecticidally effective amount of the above composition to the locus ofcrops, or other areas where insects are present or are expected to bepresent.

DETAILED DESCRIPTION OF THE INVENTION

One aspect of the present invention is insecticidal compositionscomprising at least one of an insecticidally effective amount of acompound of formula I and at least one insecticidally compatible carriertherefor, wherein the compound of formula I is:

wherein

-   R¹ through R⁸, inclusively, are independently selected from    hydrogen, halogen, alkyl, cycloalkyl, alkenyl, alkynyl,    trialkylsilylalkynyl, alkoxy, haloalkyl, haloalkoxy, alkylthio,    alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl,    haloalkylsulfonyl, dialkylaminosulfonyl, nitro, cyano, amino,    formyl, or alkylcarbonyl;-   X is selected from —CR⁹R¹⁰—, —CR¹¹R¹²CR¹³R¹⁴—, —CR¹⁵═CR¹⁶—, —NR¹⁷—,    —CR¹⁸R¹⁹NR²⁰—, or —CR²¹═N—;    and-   Y is selected from —CR²²R²³—, —CR²⁴R²⁵CR²⁶R²⁷—, —CR²⁸═CR²⁹, —N³⁰,    —CR³¹R³²NR²²—, —O—, —S—, —S(O)—, —S(O)₂—, —CR³⁴R³⁵O—, —CR³⁶R³⁷S—, or    —CR³⁸═N—;    where-   R⁹ and R¹⁰ are independently selected from hydrogen, alkyl, or    (piperidin-4-yl)alkyl;    or-   R⁹ and R¹⁰ may be taken together with    or with ═CHC₂H₄NR⁴⁰R⁴¹,    where-   R³⁹, R⁴⁰ and R⁴¹ are independently selected from hydrogen; alkyl;    hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl, wherein aryl is optionally substituted with    one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁴⁰ and R⁴¹ may be taken together with —C₂H₄N(CH₃)C₂H₄— to form a    piperazine ring;-   u is 0 or 1,-   and when u is 1, an N-oxide is formed;-   n is 0, and R^(a) is hydrogen;    or-   n is 1 to 8, and R^(a) is selected from one or more of alkyl,    alkoxyalkyl, alkoxycarbonyl, and aryl, wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R¹¹ is selected from hydrogen, alkyl, alkylaminoalkoxy,    dialkylaminoalkoxy, N(alkyl)(alkylaminoalkyl),    N(alkyl)(dialkylaminoalkyl), alkylaminoalkylalkynyl,    dialkylaminoalkylalkynyl, morpholinyl, imidazolinyl,    alkylpyrrolidinyloxy,    where-   v is 0 or 1,    and when v is 1, A is abridging group selected from —O—, —S—, —NH—,    and —CH₂—;-   u is as described above;-   R⁴² through R⁴⁵, inclusively, are independently selected from    hydrogen; alkyl; alkenyl; alkynyl; hydroxylalkyl; alkoxyalkyl;    alkylthioalkyl; alkylcarbonyl; alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl; heteroaryl; heteroarylalkyl;    heteroarylalkylamino; wherein aryl and heteroaryl are optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁴³ and R⁴⁴ may be taken together with —C₅H₁₀— to form a piperidine    ring;-   m, p, and q are 0, and R^(b), R^(c) and R^(d) are hydrogen;    or-   m is 1 to 8, p is 1 to 7, and q is 1 to 10, and R^(b), R^(c), and    R^(d), respectively, are independently selected from one or more of    alkyl, alkoxyalkyl, alkylamino, dialkylamino, alkoxycarbonyl, or    aryl, wherein aryl is optionally substituted with one or more    halogen, alkoxy, haloalkyl, or aryl;    or-   R¹¹ and R¹² may be taken together with    where R^(a), n, u, and R³⁹ are as described above;-   R¹², when not taken together with R¹¹, and R¹³, R¹⁴, and R¹⁶, are    independently selected from hydrogen, hydroxy, halogen, alkyl,    alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,    alkoxycarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl,    alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylaminosulfonyl,    or dialkylaminosulfonyl;-   R¹⁵ is selected from    where m, u, v, A, R^(b) and R⁴² are as described above;-   R¹⁷ is hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or —C₃H₆N⁴⁷R^(48 where)-   A, v, and u are as described above;-   R⁴⁶ is selected from selected from hydrogen; alkyl; alkenyl;    alkynyl; hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl;    alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;    arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl;    heteroarylalkyl; heteroarylalkylamino; wherein aryl and heteroaryl    are optionally substituted with one or more halogen, alkoxy,    haloalkyl, or aryl;-   R⁴⁷ and R⁴⁸ are independently selected from hydrogen and alkyl;    or-   R⁴⁷ and R⁴⁸ may be taken together with —C₅H₁₀— to form a piperidine    ring, or with —C₂H₄N(CH₃)C₂H₄—, or —C₂H₄N(C₂H₄OH)C₂H₄— to form a    piperazine ring;-   R¹⁸ and R¹⁹ are independently selected from hydrogen, alkyl, amino,    alkylaminoalkyl, and dialkylaminoalkyl;-   R²⁰ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R²¹ is selected from hydrogen, alkyl,    where-   A, v, and u are as described above;-   R⁴⁹ through R⁵², inclusively, are independently selected from    hydrogen; alkyl; alkenyl, alkynyl, hydroxylalkyl; alkoxyalkyl;    alkylthioalkyl; alkylcarbonyl, alkoxycarbonylalkyl;    haloalkoxycarbonyl; arylalkyl; aryloxyalkyl; arylcarbonylalkyl;    arylcarbonyloxyalkyl, heteroaryl, heteroarylalkyl,    heteroarylalkylamino, wherein aryl and heteroaryl are optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;    or-   R⁵⁰ and R⁵¹ may be taken together with —C₅H₁₀— to form a piperidine    ring;-   r, s, and t are 0, and R^(e), R^(f), and R^(g) are hydrogen,    or-   r is 1 to 8, s is 1 to 7, t is 1 to 10, and R^(e), R^(f), and R^(g),    respectively, are independently selected from one or more of alkyl,    alkoxyalkyl, alkylamino, dialkylamino, alkoxycarbonyl, or aryl,    wherein aryl is optionally substituted with one or more halogen,    alkoxy, haloalkyl, or aryl;-   R²² through R²⁹, inclusively, are independently selected from    hydrogen, and alkyl;-   R³⁰ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R³¹ and R³² are independently selected from hydrogen, and alkyl,-   R³³ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;    dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;    alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionally    substituted with one or more halogen, alkoxy, haloalkyl, or aryl;-   R³⁴ through R³⁸, inclusively, are independently selected from    hydrogen, and alkyl;    and,    agriculturally acceptable salts thereof.

Preferred insecticidal compositions of the present invention arecomprised of compounds of formula I, wherein X is —CR⁹R¹⁰— and Y isselected from —O—, —S—, —CR²²R²³—, and CR³⁴R³⁵O—;

where

-   R⁹ and R¹⁰ are taken together with    where-   R³⁹ is selected from hydrogen; alkyl; hydroxylalkyl; alkoxyalkyl;    alkylthioalkyl; alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl;    aryloxyalkyl; arylcarbonylalkyl; arylcarbonyloxyalkyl, wherein aryl    is optionally substituted with one or more halogen, alkoxy,    haloalkyl, or aryl;    and,-   R²², R², R³⁴ and R³⁵ are independently selected from hydrogen and    alkyl.

Other preferred insecticidal compositions of the present invention arecomprised of compounds of formula I, wherein X is —CR¹¹R¹²CR¹³R¹⁴— and Yis selected from —O—, —S— and —CR²²R²³;

where

-   R¹¹ is selected from    where-   R⁴² and R⁴⁵ are independently selected from hydrogen; alkyl;    alkenyl; alkynyl; hydroxylalkyl; alkoxyalkyl; alkylthioalkyl;    alkylcarbonyl; alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl;    aryloxyalkyl; arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl;    heteroarylalkyl; heteroarylalkylamino; wherein aryl and heteroaryl    are optionally substituted with one or more halogen, alkoxy,    haloalkyl, or aryl;-   R¹² is selected from selected from hydrogen, hydroxy, halogen,    alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,    alkoxycarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl,    alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylaminosulfonyl,    and dialkylaminosulfonyl;-   R¹³ and R¹⁴ are hydrogen; and,-   R²² and R²³ are independently selected from hydrogen and alkyl.

Yet other preferred insecticidal compositions of the present inventionare comprised of compounds of formula I, wherein X is —CR¹⁸R¹⁹NR²⁰— andY is selected from —O—, —S— and —CR²²R²³;

where

-   R²⁰ is selected from hydrogen, alkyl, alkoxyalkyl, alkoxycarbonyl,    dialkylaminoalkyl, alkylaminocarbonyl, and dialkylaminocarbonyl;    and,-   R²² and R²³ are independently selected from hydrogen and alkyl.

Yet still other preferred insecticidal compositions of the presentinvention are comprised of compounds of formula I, wherein X is —R²¹═N—and Y is selected from —S— and —CR²²R²³—;where R²¹ is

where

-   R⁴⁹ is selected from hydrogen; alkyl; alkenyl, alkynyl,    hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl,    alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;    arylcarbonylalkyl; arylcarbonyloxyalkyl, heteroaryl,    heteroarylalkyl, heteroarylalkylamino, wherein aryl and heteroaryl    are optionally substituted with one or more halogen, alkoxy,    haloalkyl, or aryl;    and,-   R²² and R²³ are independently selected from hydrogen and alkyl.

One skilled in the art will, of course, recognize that certaincombinations of X and Y as set forth above, for example, when X is—CR⁹R¹⁰— and Y is —NR³⁰—, or when X is —NR¹⁷— and Y is —CR²²R²³—, maylead to duplicity of compounds of formula I. Such duplicity of compoundsis outside the scope of the present invention.

Certain compounds within the scope of formula I, which find utility inthe novel insecticidal compositions of the present invention, may be newand novel compositions of matter. In addition, in certain cases thecompounds within the scope of formula I may possess asymmetric centers,which can give rise to optical enantiomorphs and diastereomers.Compounds within the scope of formula I may exist in two or more forms,i.e., polymorphs, which are significantly different in physical andchemical properties. Compounds within the scope of formula I may alsoexist as tautomers, which are in equilibrium. Compounds within the scopeof formula I may also possess acidic or basic moieties, which may allowfor the formation of agriculturally acceptable salts or agriculturallyacceptable metal complexes.

This invention includes the use of such enantiomorphs, polymorphs,tautomers, salts and metal complexes. Agriculturally acceptable saltsand metal complexes include, without limitation, for example, ammoniumsalts, the salts of organic and inorganic acids, such as hydrochloricacid, sulfonic acid, ethanesulfonic acid, trifluoroacetic acid,methylbenzenesulfonic acid, phosphoric acid, gluconic acid, pamoic acid,and other acid salts, and the alkali metal and alkaline earth metalcomplexes with, for example, sodium, potassium, lithium, magnesium,calcium, and other metals.

The methods of the present invention are predicated on causing aninsecticidally effective amount of a compound of formula I to be presentwithin insects in order to kill or control the insects. Preferredinsecticidally effective amounts are those that are sufficient to killthe insect. It is within the scope of the present invention to cause acompound of formula I to be present within insects by contacting theinsects with a derivative of that compound, which derivative isconverted within the insect to a compound of formula I. This inventionincludes the use of such compounds, which can be referred to aspro-insecticides.

Another aspect of the present invention relates to compositionscontaining an insecticidally effective amount of at least one compoundof formula I, and, optionally, an effective amount of at least onesecond compound, with at least one insecticidally compatible carriertherefor.

Another aspect of the present invention relates to methods ofcontrolling insects by applying an insecticidally effective amount of acomposition set forth above to a locus of crops such as, withoutlimitation, cereals, cotton, vegetables, and fruits, or other areaswhere insects are present or are expected to be present.

The present invention also includes the use of the compounds andcompositions set forth herein for control of non-agricultural insectspecies, for example, dry wood termites and subterranean termites; aswell as for use as pharmaceutical agents and compositions thereof.

As used in this specification and unless otherwise indicated thesubstituent terms “alkyl”, “alkenyl”, “alkynyl”, “alkoxy”, “alkenyl”,and “alkynyl” used alone or as part of a larger moiety, includesstraight or branched chains of at least one or two carbon atoms, asappropriate to the substituent, and preferably up to 12 carbon atoms,more preferably up to ten carbon atoms, most preferably up to sevencarbon atoms, wherein “alkenyl” has at least one carbon to carbon doublebond, and “alkynyl” has at least one carbon to carbon triple bond. Theterm “aryl” refers to an aromatic ring structure, including fused rings,having four to ten carbon atoms, for example, phenyl and naphthyl. Theterm “heteroaryl” refers to an aromatic ring structure, including fusedrings, having four to ten carbon atoms, and in which one or more of theatoms in the ring is other than carbon, for example, sulfur, oxygen, ornitrogen. The term “THF” refers to tetrahydrofuran. The term “DMF”refers to N,N-dimethylformamide. The term “halogen” or “halo” refers tofluorine, bromine, iodine, or chlorine. The term “ambient temperature”or “room temperature” often abbreviated as “RT”, for example, inreference to a chemical reaction mixture temperature, refers to atemperature in the range of 20° C. to 30° C. The term “insecticidalcomposition” refers to a composition containing an insecticide capableof killing an insect pest. The term “insecticidally effective amount”refers a composition containing an insecticide that is applied at a rateof application of insecticide sufficient to kill an insect pest.

The tricyclic derivatives of formula I can be synthesized by methodsthat are individually known to one skilled in the art from intermediatecompounds readily available in commerce. Scheme 1 below illustrates ageneral procedure for synthesizing tricyclic derivatives of formula I,where, for example, X is —CR⁹R¹⁰—, and Y is —O— or —S—, where R⁹ and R¹⁰are taken together with

As depicted in Scheme 1, compounds of formula I, for example, where X is—CR⁹R¹⁰—, and Y is —O— or —S—, and where R⁹ and R¹⁰ are taken togetherwith

were prepared in one-step syntheses by reacting, for example,thioxanthen-9-one (Y is —S—), 1-methyl-4-piperidone, titanium(IV)chloride, and zinc in an appropriate solvent, affording thecorresponding 10-(1-methyl-4-piperidylidene)benzo[b,e]thiane, a compoundof formula I.

Other compounds of formula I were prepared in multi-step syntheses, forexample, xanthone (Y is —O—), was reacted with1-phenylmethyl-4-piperidone, zinc, and titanium(IV) chloride in anappropriate solvent, as set forth above, yielding the corresponding9-(1-phenylmethyl-4-piperidylidene)xanthene. The xanthene intermediatewas, in turn, reacted with 2,2,2-trichloroethyl chloroformate in anappropriate solvent, affording the corresponding9-[1-(2,2,2-trichloroethoxycarbonyl)-4-piperidylidene]xanthene (Ia).Intermediate (Ia) was then treated with a strong base for example,sodium hydroxide, and an appropriate alcohol, such as methanol, yieldingthe corresponding 9-(1-methoxycarbonyl-4-piperidylidene)xanthene (Ib),which was, in turn, reduced with, for example, lithium aluminum hydridein an appropriate solvent, affording9-(1-methyl-4-piperidylidene)xanthene, a compound of formula I.

Scheme 2 below illustrates a general procedure for synthesizingtricyclic derivatives of formula I, where, for example, X is —CR²¹═N—and and Y is —O— or —S—, where R²¹ is

As depicted in Scheme 2, those compounds of formula I, for example,where X is —CR²¹═N— and Y is —O— or —S—, were also prepared inmulti-step syntheses. For example, the known amine,2-[4-(methylethyl)phenylthio]phenylamine (Y is S), was reacted withtrichloromethyl chloroformate in an appropriate solvent, affording thecorresponding isocyanate IIa. Intermediate IIa was in turn cyclized withaluminum chloride in an appropriate high-boiling solvent such aschlorobenzene, yielding the corresponding cyclized ketone derivativeIIb, for example2-(methylethyl)-10-dibenzo[b,f]-1,4-thiazaperhydroepin-11-one.Intermediate IIb was then chlorinated with, for example, phosphorousoxychloride in the presence of a base catalyst, providing thecorresponding chloride derivative IIc. The so-prepared chloridederivative IIc, for example,11-chloro-2-(methylethyl)dibenzo[b,f]1,4-thiazepine, was then convertedto compounds of formula I by reacting it with an appropriate amine, forexample 1-methylpiperazine, providing the compound2-(methylethyl)-11-(4-methylpiperazinyl)dibenzo[b,f]1,4-thiazepine I.

Scheme 3 below illustrates a general procedure for synthesizingtricyclic derivatives of formula I, where, for example, X isCR¹¹R¹²CR¹³R¹⁴ and Y is —O— or —S—, and R¹¹ and R¹² represent a numberof moieties.

As depicted in Scheme 3, those compounds of formula I, for example,where X is —CR¹¹R¹²CR¹³R¹⁴— and Y is —O— or —S—, were again prepared inmulti-step syntheses. For example, an appropriately substituted aceticacid derivative, such as2-{2-[4-(trifluoromethoxy)phenylthio]phenyl}acetic acid, was cyclizedwith Eaton's Reagent affording the corresponding ketone derivative IIIa,for example, 8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-one.Intermediate 1a was first reduced to the corresponding alcohol bytreatment of IIIa with sodium borohydride in an appropriate solvent,then the alcohol was chlorinated with thionyl chloride, yielding thecorresponding chloro derivative IIIb. The so-prepared chloridederivative IIIb, for example,11-chloro-2-(trifluoromethoxy)-10H,11H-dibenzo[b,f]thiepane, was thenconverted to compounds of formula I by reacting it with an appropriateamine, for example 1-methylpiperazine, providing the compound1-(4-methylpiperazinyl)-2-(trifluoromethoxy)-10H,11H-dibenzo[b,f]thiopane I.

Alternatively, the ketone intermediate IIIa may be reacted directly withan appropriate base to provide additional compounds of formula I. Forexample, 8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-one IIIa, asset forth above, may be reacted under basic conditions withhalogen-containing compound, such as 4-bromopyridine, in an appropriatesolvent, providing a compound of formula I, for example,10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol.

Any compound of formula I containing an alcohol moiety may be furtherreacted to prepare yet other compounds of formula I. For example,10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol, asset forth above, was alkylated with an alkyl halide, such as methyliodide, then reduced with a reducing agent in an appropriate solvent,yielding the corresponding alkyl derivative, a compound of formula I,for example,10-(1-methyl(4-1,2,5,6-tetrahydropyridyl))-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-olI.

In yet another method, a compound of formula I containing an alcoholmoiety, such as10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol, asset forth above, may be reacted with, for example, (diethylamino)sulfurtrifluoride in an appropriate solvent, affording yet other compounds offormula I, for example,10-fluoro-10-(4-pyridyl)-8-(trifluoromethoxy)-1H-dibenzo[b,f]thiepane.

Examples 1 through 7, inclusively, set forth below, provide in detailthe methods by which compounds of formula I were prepared.

One skilled in the art will, of course, recognize that the formulationand mode of application of a toxicant may affect the activity of thematerial in a given application. Thus, for agricultural use the presentinsecticidal compounds may be formulated as a granular of relativelylarge particle size (for example, 8/16 or 4/8 US Mesh), as water-solubleor water-dispersible granules, as powdery dusts, as wettable powders, asemulsifiable concentrates, as aqueous emulsions, as solutions, or as anyof other known types of agriculturally-useful formulations, depending onthe desired mode of application. It is to be understood that the amountsspecified in this specification are intended to be approximate only, asif the word “about” were placed in front of the amounts specified.

These insecticidal compositions may be applied either as water-dilutedsprays, or dusts, or granules to the areas in which suppression ofinsects is desired. These formulations may contain as little as 0.1%,0.2% or 0.5% to as much as 95% or more by weight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, flours such aswalnut shell and cottonseed flours, and other organic and inorganicsolids which act as dispersants and carriers for the toxicant; thesefinely divided solids have an average particle size of less than about50 microns. A typical dust formulation useful herein is one containing1.0 part or less of the insecticidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for insecticides, are in theform of finely divided particles that disperse readily in water or otherdispersant. The wettable powder is ultimately applied to the locus whereinsect control is needed either as a dry dust or as an emulsion in wateror other liquid. Typical carriers for wettable powders include Fuller'searth, kaolin clays, silicas, and other highly absorbent, readily wetinorganic diluents. Wettable powders normally are prepared to containabout 5-80% of active ingredient, depending on the absorbency of thecarrier, and usually also contain a small amount of a wetting,dispersing or emulsifying agent to facilitate dispersion. For example, auseful wettable powder formulation contains 80.0 parts of theinsecticidal compound, 17.9 parts of Palmetto clay, and 1.0 part ofsodium lignosulfonate and 0.3 part of sulfonated aliphatic polyester aswetting agents. Additional wetting agent and/or oil will frequently beadded to a tank mix for to facilitate dispersion on the foliage of theplant.

Other useful formulations for insecticidal applications are emulsifiableconcentrates (ECs) which are homogeneous liquid compositions dispersiblein water or other dispersant, and may consist entirely of theinsecticidal compound and a liquid or solid emulsifying agent, or mayalso contain a liquid carrier, such as xylene, heavy aromatic naphthas,isphorone, or other non-volatile organic solvents. For insecticidalapplication these concentrates are dispersed in water or other liquidcarrier and normally applied as a spray to the area to be treated. Thepercentage by weight of the essential active ingredient may varyaccording to the manner in which the composition is to be applied, butin general comprises 0.5 to 95% of active ingredient by weight of theinsecticidal composition.

Flowable formulations are similar to ECs, except that the activeingredient is suspended in a liquid carrier, generally water. Flowables,like ECs, may include a small amount of a surfactant, and will typicallycontain active ingredients in the range of 0.5 to 95%, frequently from10 to 50%, by weight of the composition. For application, flowables maybe diluted in water or other liquid vehicle, and are normally applied asa spray to the area to be treated.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, but are not limited to, the alkyl and alkylarylsulfonates and sulfates and their sodium salts; alkylaryl polyetheralcohols; sulfated higher alcohols; polyethylene oxides; sulfonatedanimal and vegetable oils; sulfonated petroleum oils; fatty acid estersof polyhydric alcohols and the ethylene oxide addition products of suchesters; and the addition product of long-chain mercaptans and ethyleneoxide. Many other types of useful surface-active agents are available incommerce. Surface-active agents, when used, normally comprise 1 to 15%by weight of the composition.

Other useful formulations include suspensions of the active ingredientin a relatively non-volatile solvent such as water, corn oil, kerosene,propylene glycol, or other suitable solvents.

Still other useful formulations for insecticidal applications includesimple solutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the toxicant is carried on relative coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low-boiling dispersant solvent carrier mayalso be used. Water-soluble or water-dispersible granules are freeflowing, non-dusty, and readily water-soluble or water-miscible. In useby the farmer on the field, the granular formulations, emulsifiableconcentrates, flowable concentrates, aqueous emulsions, solutions, etc.,may be diluted with water to give a concentration of active ingredientin the range of say 0.1% or 0.2% to 1.5% or 2%.

The active insecticidal compounds of this invention may be formulatedand/or applied with one or more second compounds. Such combinations mayprovide certain advantages, such as, without limitation, exhibitingsynergistic effects for greater control of insect pests, reducing ratesof application of insecticide thereby minimizing any impact to theenvironment and to worker safety, controlling a broader spectrum ofinsect pests, safening of crop plants to phytotoxicity, and improvingtolerance by non-pest species, such as mammals and fish.

Second compounds include, without limitation, other pesticides, plantgrowth regulators, fertilizers, soil conditioners, or other agriculturalchemicals. In applying an active compound of this invention, whetherformulated alone or with other agricultural chemicals, an effectiveamount and concentration of the active compound is of course employed;the amount may vary in the range of, e.g. about 0.001 to about 3 kg/ha,preferably about 0.03 to about 1 kg/ha. For field use, where there arelosses of insecticide, higher application rates (e.g., four times therates mentioned above) may be employed.

When the active insecticidal compounds of the present invention are usedin combination with one or more of second compounds, e.g., with otherpesticides such as herbicides, the herbicides include, withoutlimitation, for example: N-(phosphonomethyl)glycine (“glyphosate”);aryloxyalkanoic acids such as (2,4-dichlorophenoxy)acetic acid(“2,4-D”), (4-chloro-2-methylphenoxy)acetic acid (“MCPA”),(+/−)-2-(4-chloro-2-methylphenoxy)propanoic acid (“MCPP”); ureas such asN,N-dimethyl-N′-[4-(1-methylethyl)phenyl]urea (“isoproturon”);imidazolinones such as2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-pyridinecarboxylicacid (“imazapyr”), a reaction product comprising(+/−)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-4-methylbenzoicacid and(+/−)2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methylbenzoicacid (“imazamethabenz”),(+/−)-2-[4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-ethyl-3-pyridinecarboxylicacid (“imazethapyr”), and(+/−)-2-[4,5-dihydro-4-methyl-4(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-3-quinolinecarboxylicacid (“imazaquin”); diphenyl ethers such as5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoic acid(“acifluorfen”), methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate(“bifenox”), and5-[2-chloro-4-(trifluoromethyl)phenoxy]-N-(methylsulfonyl)-2-nitrobenzamide(“fomasafen”); hydroxybenzonitriles such as4-hydroxy-3,5-diiodobenzonitrile (“ioxynil”) and3,5-dibromo-4-hydroxybenzonitrile (“bromoxynil”); sulfonylureas such as2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]arbonyl]amino]sulfonyl]benzoicacid (“chlorimuron”),2-chloro-N-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbony]benzenesulfonamide(achlorsulfuron”),2-[[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sufonyl]methyl]benzoicacid (“bensulfuron”),2-[[[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-methy-1H-pyrazol-4-carboxylicacid (“pyrazosulfuron”),3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylicacid (“thifensulfuron”), and2-(2-chloroethoxy)-N[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide(“triasulfuron”); 2-(4-aryloxyphenoxy)alkanoic acids such as(+/−)-2[4-[(6-chloro-2-benzoxazolyl)oxy]phenoxy]propanoic acid(fenoxaprop”),(+/−)-2-[4[[5-(trifluoromethyl)-2-pyridinyl]oxy]phenoxy]propanoic acid(“fluazifop”), (+/−)-2-[4-(6-chloro-2-quinoxalinyl)oxy]phenoxy]propanoicacid (“quizalofop”), and (+/−)-2-[(2,4-dichlorophenoxy)phenoxy]propanoic acid (“diclofop”);benzothiadiazinones such as3-(1-methylethyl)-1H-1,2,3-benzothiadiazin-4(3H)-one-2,2-dioxide(“bentazone”); 2-chloroacetanilides such asN-(butoxymethyl)-2-chloro-N-(2,6-diethylphenyl)acetamide (“butachlor”),2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-menthoxy-1-methylethyl)acetamide(“metolachlor”),2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)acetamide(“acetochlor”), and(RS)-2-chloro-N-(2,4-dimethyl-3-thienyl)-N-(2-methoxy-1-methylethyl)acetamide(“dimethenamide”); arenecarboxylic acids such as3,6-dichloro-2-methoxybenzoic acid (“dicamba”); pyridyloxyacetic acidssuch as [(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid(“fluroxypyr”), and other herbicides.

When the active insecticidal compounds of the present invention are usedin combination with one or more of second compounds, e.g., with otherpesticides such as other insecticides, the other insecticides include,for example: organophosphate insecticides, such as chlorpyrifos,diazinon, dimethoate, malathion, parathion-methyl, and terbufos;pyrethroid insecticides, such as fenvalerate, deltamethrin,fenpropathrin, cyfluthrin, flucythrinate, alpha-cypermethrin,biphenthrin, resolved cyhalothrin, etofenprox, esfenvalerate,tralomehtrin, tefluthiin, cycloprothrin, betacyfluthrin, andacrinathrin; carbamate insecticides, such as aldecarb, carbaryl,carbofuran, and methomyl; organochlorine insecticides, such asendosulfan, endrin, heptachlor, and lindane; benzoylurea insecticides,such as diflubenuron, triflumuron, teflubenzuron, chlorfluazuron,flucycloxuron, hexaflumuron, flufenoxuron, and lufenuron; and otherinsecticides, such as amitraz, clofentezine, fenpyroximate, hexythiazox,spinosad, and imidacloprid.

When the active insecticidal compounds of the present invention are usedin combination with one or more of second compounds, e.g., with otherpesticides such as fungicides, the fungicides include, for example:benzimidazole fungicides, such as benomyl, carbendazim, thiabendazole,and thiophanate-methyl; 1,2,4-triazole fungicides, such asepoxyconazole, cyproconazole, flusilazole, flutriafol, propiconazole,tebuconazole, triadimefon, and triadimenol; substituted anilidefungicides, such as metalaxyl, oxadixyl, procymidone, and vinclozolin;organophosphorus fungicides, such as fosetyl, iprobenfos, pyrazophos,edifenphos, and tolclofos-methyl; morpholine fungicides, such asfenpropimorph, tridemorph, and dodemorph; other systemic fungicides,such as fenarimol, imazalil, prochloraz, tricyclazole, and triforine;dithiocarbamate fungicides, such as mancozeb, maneb, propineb, zineb,and ziram; non-systemic fungicides, such as chlorothalonil,dichlofluanid, dithianon, and iprodione, captan, dinocap, dodine,fluazinam, gluazatine, PCNB, pencycuron, quintozene, tricylamide, andvalidamycin; inorganic fungicides, such as copper and sulphur products,and other fungicides.

When the active insecticidal compounds of the present invention are usedin combination with one or more of second compounds, e.g., with otherpesticides such as nematicides, the nematicides include, for example:carbofuran, carbosulfan, turbufos, aldecarb, ethoprop, fenamphos,oxamyl, isazofos, cadusafos, and other nematicides.

When the active insecticidal compounds of the present invention are usedin combination with one or more of second compounds, e.g., with othermaterials such as plant growth regulators, the plant growth regulatorsinclude, for example: maleic hydrazide, chlormequat, ethephon,gibberellin, mepiquat, thidiazon, inabenfide, triaphenthenol,paclobutrazol, unaconazol, DCPA, prohexadione, trinexapac-ethyl, andother plant growth regulators.

Soil conditioners are materials which, when added to the soil, promote avariety of benefits for the efficacious growth of plants. Soilconditioners are used to reduce soil compaction, promote and increaseeffectiveness of drainage, improve soil permeability, promote optimumplant nutrient content in the soil, and promote better pesticide andfertilizer incorporation. When the active insecticidal compounds of thepresent invention are used in combination with one or more of secondcompounds, e.g., with other materials such as soil conditioners, thesoil conditioners include organic matter, such as humus, which promotesretention of cation plant nutrients in the soil; mixtures of cationnutrients, such as calcium, magnesium, potash, sodium, and hydrogencomplexes; or microorganism compositions which promote conditions in thesoil favorable to plant growth. Such microorganism compositions include,for example, bacillus, pseudoinonas, azotobacter, azospirillum,rhizobiurn, and soil-borne cyanobacteria.

Fertilizers are plant food supplements, which commonly contain nitrogen,phosphorus, and potassium. When the active insecticidal compounds of thepresent invention are used in combination with one or more of secondcompounds, e.g., with other materials such as fertilizers, thefertilizers include nitrogen fertilizers, such as ammonium sulfate,ammonium nitrate, and bone meal; phosphate fertilizers, such assuperphosphate, triple superphosphate, ammonium sulfate, and diammoniumsulfate; and potassium fertilizers, such as muriate of potash, potassiumsulfate, and potassium nitrate, and other fertilizers.

The following examples further illustrate the present invention, but, ofcourse, should not be construed as in any way limiting its scope. Theexamples are organized to present protocols for the synthesis of thecompounds of formula I of the present invention, set forth a list ofsuch synthesized species, and set forth certain biological dataindicating the efficacy of such compounds.

EXAMPLE 1

This example illustrates one protocol for the preparation of10-(1-methyl-4-piperidylidene)benzo[b,e]thiane (Compound 2 in tablebelow) Under a nitrogen atmosphere, 45 mL of stirred THF was cooled inan ice-water bath. To this was added 8 mL (0.008 mole) of titanium(IV)chloride (1.0M solution in toluene) via a syringe, then 1.0 gram (0.016mole) of zinc was added in two portions during a five-minute period.After this time the reaction mixture was stirred during a ten-minuteperiod, then a solution of 0.76 gram (0.0036 mole) of thioxanthen-9-oneand 0.56 gram (0.005 mole) of 1-methyl-4-piperidone in 20 mL of THF wasadded drop-wise during a ten-minute period. Upon completion of addition,the reaction mixture was stirred for ten minutes, then it was heated to60° C. where it stirred for about 20 hours. After this time, thereaction mixture was cooled and poured into 50 mL of an aqueous 10%solution of potassium carbonate. The mixture was stirred for about 20minutes, then 50 mL of ethyl acetate was added and the mixture wasstirred for an additional 20 minutes. The mixture was then filteredthrough a pad of diatomaceous earth, and the diatomaceous earth pad waswashed with 50 mL of ethyl acetate. The combined ethyl acetate from thewash and from the filtrate was separated, and the aqueous phase wasextracted with 20 mL of ethyl acetate. The combined ethyl acetatefractions were then washed with an aqueous solution saturated withsodium bicarbonate and dried with sodium sulfate. The mixture wasfiltered and the filtrate concentrated under reduced pressure to a solidresidue. The residue was purified with column chromatography on aluminumoxide (neutral activated III) using mixtures of heptane and ethylacetate as eluant. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 0.25 gram of the Compound2. The NMR spectrum was consistent with the proposed structure.

EXAMPLE 2

This example illustrates one protocol for the preparation of9-(1-methyl-4-piperidylidene)xanthene (Compound 8 in table below)

Step A Synthesis of 9-(1-phenylmethyl-4-piperidylidene)xanthene as anintermediate

This compound was prepared in a manner analogous to that set forth inExample 1, by the reaction of 0.78 gram (0.004 mole) of xanthone, 0.95gram (0.005 mole) of 1-phenylmethyl-4-piperidone, 1.6 grams (0.024 mole)of zinc, and 12 mL (0.012 mole) of titanium(IV) chloride (1.0M solutionin toluene) in 70 mL of THF. The yield of the subject compound was 1.4grams. The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of9-[1-(2,2,2-trichloroethoxycarbonyl)-4-piperidylidene]xanthene as anintermediate

Under a nitrogen atmosphere, a solution of 0.7 gram (0.002 mole) of9-(1-phenylmethyl-4-piperidylidene)xanthene in 50 mL of 1:2 chloroform:acetonitrile was stirred, and 0.85 gram (0.004 mole) of2,2,2-trichloroethyl chloroformate was added in one portion via asyringe. Upon completion of addition, the reaction mixture was warmed toreflux where it stirred for one hour, then the reaction mixture wascooled to ambient temperature where it stirred for about 18 hours. Afterthis time the reaction mixture was poured into 50 mL of water andextracted with two 40 mL portions of ethyl acetate. The combinedextracts were then washed with an aqueous solution saturated with sodiumchloride and dried with sodium sulfate. The mixture was filtered and thefiltrate was concentrated under reduced pressure to a residual oil. Theoil was dissolved in 20 mL of methanol, to which was added 5 mL ofwater. The mixture was cooled in an ice-water bath, and a solidprecipitate formed. The solid was collected by filtration and driedunder vacuum, yielding 0.73 gram of the subject compound, mp 132-134° C.The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 9-(1-methoxycarbonyl-4-piperidylidene)xanthene as anintermediate

A stirred solution of 0.6 gram (0.0013 mole) of9-[1-(2,2,2-trichloroethoxycarbonyl)-4-piperidylidene]xanthene, 0.25gram (0.0062 mole) of sodium hydroxide, and 2 mL of water in 20 mL ofmethanol was warmed to reflux where it stirred for six hours. After thistime the reaction mixture was cooled to ambient temperature where itstirred for about 18 hours. The reaction mixture was then concentratedunder reduced pressure to remove the majority of the methanol, and 30 mLof an aqueous solution saturated with sodium bicarbonate was added. Themixture was extracted with two 20 mL portions of ethyl acetate and thecombined extracts were dried with sodium sulfate. The mixture wasfiltered and the filtrate was concentrated under reduced pressure to anoil residue. The residue was purified with column chromatography onsilica using 5:1 heptane:ethyl acetate as eluant. The appropriatefractions were combined and concentrated under reduced pressure,yielding 0.28 gram of the subject compound. The NMR spectrum wasconsistent with the proposed structure.

Note: The intended intermediate of Step C in the above preparativeexample was 9-(4-piperidylidene)xanthene.

Step D Synthesis of Compound 8

Under a nitrogen atmosphere a solution of 0.28 gram (0.0008 mole) of9-(1-methoxycarbonyl-4-piperidylidene)xanthene in 20 mL of THF wasstirred, and 3 mL of lithium aluminum hydride (1.0M in THF) was addedvia a syringe during a ten minute period. After this time the reactionmixture was warmed to 40° C. where it stirred for two hours. Thereaction mixture was then cooled and 20 mL of aqueous 0.5N sodiumhydroxide was added in one portion. The mixture was extracted with two40 mL portions of ethyl acetate, and the combined extracts were washedwith 20 mL of an aqueous solution saturated with sodium bicarbonate. Theextracts were dried with sodium sulfate and filtered. The filtrate wasconcentrated under reduced pressure, yielding 0.2 gram of Compound 5.The NMR spectrum was consistent with the proposed structure.

EXAMPLE 3

This example illustrates one protocol for the preparation of2-(methylethyl)-11-(4-methylpiperazinyl)dibenzo[b,f]1,4-thiazepine(Compound 193 in table below)

Step A Synthesis of 2-[4-(methylethyl)phenylthio]benzenisocyanate as anintermediate

Under a nitrogen atmosphere a solution of 1.2 grams (0.0049 mole) of2-[4-(methylethyl)phenylthio]phenylamine (known compound) in 60 mL ofethyl acetate was stirred, and 2.2 grams (0.011 mole) of trichloromethylchlorooate was added by pipette in one portion. Upon completion ofaddition the reaction mixture was heated to reflux where it stirred forthree hours. After this time the reaction mixture was cooled andconcentrated under reduced pressure to a residue. The residue wasfurther dried under vacuum, yielding 1.5 grams of the subject compound.The NMR spectrum was consistent with the proposed structure.

Step B Synthesis of2-(methylethyl)-10-dibenzo[b,f]-1,4-thiazaperhydroepin-11-one as anintermediate

Under a nitrogen atmosphere a stirred mixture of 1.0 gram (0.0075 mole)of aluminum chloride in five mL of chlorobenzene was warmed to 80° C.,and a solution of 1.4 grams (0.0052 mole) of2-[4-(methylethyl)phenylthio]benzenisocyanate in one mL of chlorobenzenewas added dropwise during a one minute period. Upon completion ofaddition the reaction mixture was warmed to 110° C. where it stirred fortwo hours. After this time the reaction mixture was cooled and pouredinto water. The mixture was extracted with two 40 mL portions of ethylacetate, and the extracts were combined. The combined extracts were thenwashed with an aqueous solution saturated with sodium chloride, driedwith sodium sulfate, filtered; and the filtrate was concentrated underreduced pressure to a residue. The residue was purified with columnchromatography on silica using 5:1 and 3:1 mixtures of heptane:ethylacetate as eluants. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 0.65 gram of the subjectcompound. The NMR spectrum was consistent with the proposed structure.

Step C Synthesis of 1]-chloro-2-(methylethyl)dibenzo[b,f]1,4-thiazepineas an intermediate

Under a nitrogen atmosphere a solution of 0.62 gram (0.0023 mole) of2-(methylethyl)-10-dibenzo[b,f]-1,4-thiazaperhydroepin-11-one in 10 mLof phosphorous oxychloride was stirred and 5 drops of diethylphenylaminewas added. Upon completion of addition the reaction mixture was heatedto reflux where it stirred for 3.5 hours. The reaction mixture was thenconcentrated under reduced pressure to remove the majority of thephosphorous oxychloride, and the residue was poured into 50 mL ofice-water. The mixture was then extracted three 30 mL portions ofdiethyl ether. The combined extracts were washed with an aqueoussolution saturated with sodium chloride, dried with sodium sulfate,filtered; and the filtrate was concentrated under reduced pressure,yielding 0.55 gram of the subject compound. The NMR spectrum wasconsistent with the proposed structure.

Step D Synthesis of Compound 193

Under a nitrogen atmosphere a stirred solution of 0.24 gram (0.0008mole) of 11-chloro-2-(methylethyl)dibenzo[b,f]1,4-thiazepine and 0.4 mL(0.0036 mole) of 1-methylpiperazine in 25 mL of xylenes was heated toreflux where it stirred for two hours. After this time the reactionmixture was cooled ambient temperature and poured into 25 mL of diethylether. The mixture was then extracted with three 20 mL portions ofaqueous 3N hydrochloric acid. The aqueous extracts were combined andwashed with 20 mL of diethyl ether, made basic with aqueous 10%potassium carbonate; then extracted with three 20 mL portions of diethylether. The ether extracts were combined, dried with sodium sulfate,filtered and concentrated under reduced pressure to a residue. Theresidue was purified with column chromatography on silica usingmethylene chloride, 1% methanol in methylene chloride, and 3% methanolin methylene chloride as eluants. The appropriate fractions werecombined and concentrated under reduced pressure, yielding 0.21 gram ofCompound 193. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 4

This example illustrates one protocol for the preparation of11-(4-methylpiperazinyl)-2-(trifluoromethoxy)-10H,11H-dibenzo[b,f]thiopane (Compound 106 in table below)

Step A Synthesis of 2-{2-[4-(trifluoromethoxy)phenylthio]phenyl}aceticacid as an intermediate

A mixture of 26.2 grams (0.47 mole) of potassium hydroxide and 1.1 grams(0.018 mole) of powdered copper (catalyst) in 200 mL of water wasstirred, and 30.6 grams (0.117 mole) of 2-iodophenylacetic acid and 22.7grams (0.117 mole) of 4-trifluoromethoxyphenol were added. Uponcompletion of addition the reaction mixture was warmed to reflux whereit stirred for about 18 hours. After this time the reaction mixture wascooled to ambient temperature and filtered. The filtrate was poured into500 mL of aqueous 10% hydrochloric acid and the mixture was extractedwith three 250 mL portions of ethyl acetate. The combined extractswashed with an aqueous solution saturated with sodium chloride, driedwith sodium sulfate, filtered, and concentrated under reduced pressure,yielding 39.6 grams of the subject compound.

Step B Synthesis of 8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-oneas an intermediate

A mixture of 10.0 grams (0.0304 mole) of2-{2-[4-(trifluoromethoxy)phenylthio]phenyl}acetic acid in 75 mL ofEatons Reagent was stirred for an 18 hour period during which timecomplete solution was obtained. After this time the reaction mixture waspoured into ice-water and extracted with four 150 mL portions of ethylacetate. The combined extracts were then washed with one portion of aaqueous dilute solution of sodium bicarbonate and with one portion of anaqueous solution saturated with sodium chloride. The organic layer wasdried with sodium sulfate, filtered and concentrated under reducedpressure to a residue. The residue was purified with columnchromatography on silica using 1:2 ethyl acetate:hexane as an eluant.The appropriate fractions were combined and concentrated under reducedpressure, yielding 4.0 grams of the subject compound. The NMR spectrumwas consistent with the proposed structure. Step C Synthesis of11-chloro-2-(trifluoromethoxy)-10H,11H-dibenzo[b,f]thiepane as anintermediate

A solution of 2.3 grams (0.0073 mole) of8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-one in a mixture of 5 mLof THF and 30 mL of methanol was stirred and 0.4 gram of sodiumborohydride was added. The reaction mixture was then stirred at ambienttemperature during a two hour period. After this time the reactionmixture was poured into 100 mL of aqueous 10% hydrochloric acid, towhich was then added 300 mL of an aqueous solution saturated with sodiumchloride. The mixture was extracted with three 100 mL portions of ethylacetate. The combined extracts were dried with sodium sulfate, filteredand the filtrate concentrated under reduced pressure to a residue. In aneffort to further dry the residue, it was dissolved in 50 mL ofmethylene chloride and the mixture was concentrated under reducedpressure to a residue. The drying process was repeated two additionaltimes, yielding a dried residue. The residue was again dissolved in 50mL of methylene chloride and 3 mL of thionyl chloride was added. Thereaction mixture was stirred at ambient temperature during a 2.5 hourperiod. After this time the reaction mixture was concentrated underreduced pressure, yielding 2.0 grams of the subject compound.

Step D Synthesis of Compound 106

A solution of 1.0 gram (0.0030 mole) of11-chloro-2-(trifluoromethoxy)-10H,11H-dibenzo[b,f]thiepane wasdissolved in 5 mL of chloroform and placed in a sealable tube, followedby 1.2 grams (0.0119 mole) of 1-methylpiperazine. The sealable tube wasthen sealed and the tube and contents were heated at 80° C. during an 18hour period. The reaction mixture was taken from the tube and purifiedwith column chromatography on silica using methylene chloride, thenethyl acetate as eluants. The appropriate fractions were combined andconcentrated under reduced pressure, yielding 0.6 gram of Compound 106.The NMR spectrum was consistent with the proposed structure.

EXAMPLE 5

This example illustrates one protocol for the preparation of10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol(Compound 61 in table below)

An aliquot of 1.0 gram (0.0051 mole) of 4-bromopyridine hydrochloridewas stirred for 20 minutes with 20 mL of an aqueous solution saturatedwith sodium bicarbonate. The mixture was then extracted with two 20 mLportions of methylene chloride. The combined extracts were dried withsodium sulfate, filtered and concentrated under reduced pressure,providing 0.5 gram of the free pyridine.

Under a nitrogen atmosphere, about 0.4 grams of the free pyridine wasdissolved in 40 mL of diethyl ether and cooled to about −50° C. in a dryice-acetonitrile bath. To this cold solution was added by syringe 1.0 mL(0.0025 mole) of 2.5 M n-butyllithium (in hexanes) while maintaining thereaction mixture temperature at −45° C. or below. Upon completion ofaddition the reaction mixture was stirred for 30 minutes at −50° C.,then 0.6 gram (0.0020 mole) of8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-one (prepared in Step Bof Example 4) was added in one portion. Upon completion of addition thereaction mixture was allowed to warm to ambient temperature as itstirred during a 1.5 hour period. After this time the reaction mixturewas poured into 50 mL of water and the organic layer was separated. Theaqueous layer was extracted with two 30 mL portions of diethyl ether.The extracts and the organic layer were combined and washed with anaqueous solution saturated with sodium chloride. The combination wasthen dried with sodium sulfate, filtered and the filtrate wasconcentrated under reduced pressure to a residue. The residue waspurified with column chromatography on silica using 3:1 heptane:ethylacetate, then 1:1 heptane:ethyl acetate as eluants. The appropriatefractions were combined and concentrated under reduced pressure,yielding 0.6 gram of Compound 61. The NMR spectrum was consistent withthe proposed structure. This reaction was repeated several times.

EXAMPLE 6

This example illustrates one protocol for the preparation of10-(1-methyl(4-1,2,5,6-tetrahydropyridyl))-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol(Compound 215 in table below)

A solution of 0.55 gram (0.0014 mole) of10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol(prepared in Example 5) and 0.43 gram (0.0030 mole) of methyl iodide in60 mL of acetone was stirred in a stoppered reaction vessel for about 18hours. After this time the reaction mixture was analyzed by thin layerchromatography (TLC), which indicated some unreacted thiepan-10-ol. Anadditional 0.43 gram of methyl iodide was added to the reaction mixture,and stirring was continued for an additional 24 hours. After this timethe reaction mixture was concentrated under reduced pressure to aresidual solid, which was triturated with petroleum ether and dried. Thesolid was dissolved in 40 mL of ethanol and, with stirring, 0.45 gram(0.012 mole) of sodium borohydride was added. Upon completion ofaddition the reaction mixture was during a three hour period. After thistime the reaction mixture was poured into 75 mL of aqueous 1% sodiumbicarbonate. The mixture was then extracted with three 20 mL portions ofethyl acetate. The combined extracts were washed with an aqueoussolution saturated with sodium chloride, then dried with sodium sulfate,filtered, and concentrated under reduced pressure, yielding 0.40 gram ofCompound 215. The NMR spectrum was consistent with the proposedstructure.

EXAMPLE 7

This example illustrates one protocol for the preparation of10-fluoro-10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepane(Compound 216 in table below)

Under a nitrogen atmosphere a solution of 0.12 gram (0.0003 mole) of10-(4-pyridyl)-8-(trifluoromethoxy)-11H-dibenzo[b,f]thiepan-10-ol(prepared in Example 5) in 10 mL of methylene chloride was stirred and0.12 gram (0.0008 mole) of (diethylamino)sulfur trifluoride was added bysyringe. Upon completion of addition the reaction mixture was stirredfor a 20 minute period, then it was poured into 30 mL of an aqueousdilute solution of sodium bicarbonate. The organic layer was separatedand the aqueous layer was extracted with 25 mL of methylene chloride.The extract and the organic layer were combined and washed with anaqueous solution saturated with sodium chloride. The combination wasthen dried with sodium sulfate, filtered, and the filtrate wasconcentrated under reduced pressure to a residue. The residue waspurified with column chromatography on alumina (Neutral, Activity III)using 5:1 heptane:ethyl acetate as an eluant. The appropriate fractionswere combined and concentrated under reduced pressure, yielding 0.1 gramof Compound 216. The NMR spectrum was consistent with the proposedstructure.

It is well known to one of ordinary skill in the art that compounds likethe compounds of formula I of the present invention can containoptically active and racemic forms. It is also well known in the artthat compounds like the compounds of formula I may containstereoisomeric forms, tautomeric forms and/or exhibit polymorphism. Itis to be understood that the present invention encompasses any racemic,optically active, polymorphic, tautomeric, or stereoisomeric form, ormixtures thereof. It should be noted that it is well known in the arthow to prepare optically active forms, for example by resolution of aracemic mixture, or by synthesis from optically active intermediates.

The following table sets forth some additional examples of compounds offormula I useful in the present invention: TABLE 1 InsecticidalPhenothiazines, Phenoxazines, Dihydrophenazines, Dibenzothiepins,Dibenzooxepins, Dibenzoazepines I

Where X is —CR⁹R¹⁰—, R⁹ and R¹⁰ taken together is

where u is 0, and R^(a) is hydrogen; R¹ and R⁵ through R⁸, inclusively,are hydrogen: Cmpd. No. Y R³⁰ R² R³ R⁴ R³⁹ R^(a) n  1 S — H H H H H 0  2S — H H H CH₃ H 0  3 S — H H H CH(CH₃)₂ H 0  4 S — Cl H H CH₃ H 0  5 S —CF₃ H H CH₃ H 0  6 S — SCH₃ H H CH₃ H 0  7 S — H H H CH₂C≡N H 0  8 O — HH H CH₃ H 0  9 O — F H H CH₃ H 0  10 O — H F H CH₃ H 0  11 O — H H F CH₃H 0  12 O — C₂H₅ H H CH₃ H 0  13 O — OC₂H₅ H H CH₃ H 0  14 O — C₂H₄OCH₃H H CH₃ H 0  15 O — CF₃ H H CH₃ H 0  16 O — H OCF₃ H CH₃ H 0  17 O — ClH H CH₂Ph H 0  18 O — CF₃ H H CH₂Ph H 0  19 O — SCH₃ H H CH₂Ph H 0  20 O— H H H C₂H₄CO₂C₂H₅ H 0  21 O — H H H CH₃ 2-CH₃ 1  22 O — H H H CH₃3-CH₃ 1  23 NR³⁰ H H H H CH₃ H 0  24 NR³⁰ CH₃ H H H CH₃ H 0  25 NR³⁰ CH₃CF₃ H H CH₃ H 0 where X is —CR⁹R¹⁰—; Y is —CR³⁴R³⁵O—, and R¹, R³, R⁴,R⁵, R⁷, R⁸, R³⁴, R³⁵ are hydrogen; n is 0, and R^(a) is hydrogen: Cmpd.No. R² R⁶ R⁹ R¹⁰ R³⁹ R⁴⁰ R⁴¹  26⁶ H H

CH₃ — —  27 H CF₃

CH₃ — —  28 H CF₃

C₂H₄CO₂C₂H₅ — —  29² Cl H ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  30⁶ H Cl═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  31 H Cl ═CHC₂H₄NR⁴⁰R⁴¹ — H CH(CH₃)₂  32² OCH₃H ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  33⁶ H OCH₃ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  34⁶ HSCH₃ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  35⁶ H S(O)₂N(CH₃)₂ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃CH₃  36⁷ H SCH₃ ═CHC₂H₄NR⁴⁰R⁴¹ — —C₂H₄N(CH₃)C₂H₄— *where u is 0 where Xis —CR⁹R¹⁰—; Y is —CR³⁶R³⁷S—, and R¹ through R⁵, inclusively, R⁷, R⁸,R³⁶, and R³⁷ are hydrogen; n is 0 and R^(a) is hydrogen: Cmpd. No. R⁶ R⁹R¹⁰ R³⁹ R⁴⁰ R⁴¹  37 H

CH₃ — —  38 CF₃

CH₃ — —  39 H ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃ where u is 0 where X is —CR⁹R¹⁰—;Y is —CR³¹R³²NR³³—, where R¹ through R⁸, inclusively, and R³¹and R³² arehydrogen; and n is 0 and R^(a) is hydrogen: Cmpd. No. R⁹ R¹⁰ R³⁹ R⁴⁰ R⁴¹R³³  40 H

— — — CH₃  41

CH₃ — — CH₃  42 ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃ CH₃ where u is 0 where X is—CR⁹R¹⁰—; Y is —CR³⁸═N—, and R¹, R³ through R⁸, inclusively, and R³⁸ arehydrogen; n is 0 and R^(a) is hydrogen: Cmpd. No. R² R⁹ R¹⁰ R³⁹ R⁴⁰ R⁴¹ 43 H

CH₃ — —  44 CF₃

CH₃ — —  45 CF₃

C₂H₄CO₂C₂H₅ — —  46 H ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  47 Cl ═CHC₂H₄NR⁴⁰R⁴¹ —CH₃ CH₃  48 H ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  49 OCH₃ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃ 50 SCH₃ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃ CH₃  51 S(O)₂N(CH₃)₂ ═CHC₂H₄NR⁴⁰R⁴¹ — CH₃CH₃ *where u is 0 where X is —CR¹¹R¹²CR¹³R¹⁴—; where R¹, R³ through R⁸,inclusively, R¹³, and R¹⁴ are hydrogen, n and m are 0 and R^(a) andR^(b) are hydrogen, and when it is noted that v is 1, then A is —O—:Cmpd. No. R² R¹¹ R¹² Y R³⁹ R⁴²  52 OCF₃ OC₂H₄N(C₂H₅)₂ H S — —  53 SCH₃NHC₃H₆OC₂H₅ H S — —  54 SCH₃ N(CH₃)C₂H₄N(CH₃)₂ H S — —  55 SCH₃morpholin-4-yl H S — —  56 SCH₃

H S — CH₃ Cmpd. No. R² R¹¹ R¹² Y R³⁹ R⁴²  57 SCH₃

H S — CH₃  58 Cl imidazolin-2-yl H O — —  59 OCF₃1-methylpyrrolidin-3-yloxy H S — —  60 OCF₃ C≡CHCH₂N(CH₃)₂ OH S — —  61OCF₃

OH S — —  62 OCF₃

S CH₃ — *where u is 0 **where v is 1 where X is —CR¹¹R¹²CR¹³R¹⁴—; whereR¹², R¹³, and R¹⁴ are hydrogen; and

where v is 0; m is 0 and R^(b) is hydrogen; R⁴² is —CH₃; and unlessotherwise noted u is 0: Cmpd. No. R¹ R² R³ R⁴ R⁵ R⁶ R⁷ R⁸ Y R²² R²³ R³⁰ 63 H H H H H H H H O — — —  64 H Cl H H H H H H O — — —  65 H Br H H HH H H O — — —  66 H F H H H H H H O — — —  67 H I H H H H H H O — — — 68 H CH₃ H H H H H H O — — —  69 H CF₃ H H H H H H O — — —  70 H SCH₃ HH H H H H O — — —  71 H OCF₃ H H H H H H O — — —  72^(a) H OCF₃ H H H HH H O — — —  73 H H OCF₃ H H H H H O — — —  74^(a) H H OCF₃ H H H H H O— — —  75 H SCF₃ H H H H H H O — — —  76 H S(O)CF₃ H H H H H H O — — — 77 H S(O)₂CF₃ H H H H H H O — — —  78 H —CH═CH₂ H H H H H H O — — —  79H —C≡CH H H H H H H O — — —  80 H —C≡CSi(CH₃)₃ H H H H H H O — — —  81 HNO₂ H H H H H H O — — —  82 H Cl Cl H H H H H O — — —  83 H Cl H Cl H HH H O — — —  84 H Cl F H H H H H O — — —  85 H Cl H F H H H H O — — — 86 H F Cl H H H H H O — — —  87 H F H Cl H H H H O — — —  88 H Br H F HH H H O — — —  89 H Br H CH₃ H H H H O — — —  90² H H H H H H H H S — ——  91² H H Cl H H H H H S — — —  92 H H Cl H H Cl H H S — — —  93 F H HH H H H H S — — —  94 H H H F H H H H S — — —  95 H Cl F H H H H H S — ——  96⁸ H Cl H F H H H H S — — —  97 F H H F H H H H S — — —  98⁹ H C₂H₅H H H H H H S — — —  99 H C(CH₃)₃ H H H H H H S — — — 100 H OCH₃ H H H HH H S — — — 101 H H OCH₃ H H H H H S — — — 102 H H H OCH₃ H H H H S — —— 103² H SCH₃ H H H H H H S — — — 104⁸ H SC₂H₅ H H H H H H S — — — 105 HCF₃ H H H H H H S — — — 106 H OCF₃ H H H H H H S — — — 107^(a) H OCF₃ HH H H H H S — — — 108 H OCF₃ H H H H F H S — — — 109 H OCF₂CHF₂ H H H HH H S — — — 110² H H Cl Cl H H H H S — — — 111 H CH₃ F H H H H H S — — —112 c-C₃H₅ H H H H H H H S — — — 113 H c-C₅H₉ H H H H H H S — — — 114 HNH₂ H H H H H H S — — — 115 H C(═O)CH₃ H H H H H H S — — — 116 H H H H FH H H S — — — 117¹⁰ H H H H F H H H S — — — 118 H H H H H F H H S — — —119 H H H H H H F H S — — — 120 H H H H H H H F S — — — 121 H Cl H H H FH H S — — — 122 H SCH₃ H H H F H H S — — — 123 H SCH₃ H H H H F H S — —— 124 H SC₂H₅ H H H H F H S — — — 125⁴ H CF₃ H H H H F H S — — — 126 HOCF₃ H H H H F H S — — — 127 H CH(CH₃)₂ H H H H F H S — — — 128² HCH(CH₃)₂ H H H H F H S — — — 129 H CH(CH₃)₂ H H H H F H S(O) — — — 130 HH H H H H H H CR²²R²³ H H — 131 H OCF₃ H H H H H H CR²²R²³ H H — 132 H HH H H H H H NR³⁰ — — H 133 H F H H H H H H NR³⁰ — — H 134 H CF₃ H H H HH H NR³⁰ — — H 135 H SCH₃ H H H H H H NR³⁰ — — H 136 H OCF₃ H H H H H HNR³⁰ — — H 137 H H H H H H H H NR³⁰ — — CH₃ ^(a)u is 1, forming anN-oxide where X is —CR¹¹R¹²CR¹³R¹⁴—; where R¹², R¹³, and R¹⁴ arehydrogen; and

where v is 0; m is 0 and R^(b) is hydrogen; R³, R⁴, and R⁸ are hydrogen;and unless otherwise noted u is 0; Cmpd. No. R¹ R² R⁵ R⁶ R⁷ Y R⁴² 138 HOCF₃ H H H O H 139 H OCF₃ H H H O C₂H₅ 140 H OCF₃ H H H O C(═O)CH₃ 141 HSCH₃ H H H O 2-piperidinylethylamino 142 H H F H H S C₂H₅ 143 H OCF₃ H HH S H 144 H OCF₃ H H H S C₂H₅ 145 H OCF₃ H H H S CH₂CH═CH 146 H SCH₃ H HH S C₂H₅ 147¹⁰ H H F H H S C₂H₅ 148 H H H H H S C≡N 149⁹ H Cl H H H SC≡N 150 H CF₃ H H F S C₂H₄OH 151 H S(O)CH₃ H H F S C₂H₄OH 152 H OCH₃ H HH S C₃H₆OH 153⁴ H SCH₃ H H F S C₃H₆OH 154² H Cl H H H S C₂H₄OC₂H₅ 155 HSCH₃ H H H S CH₂CH(OH)C₂H₅ 156 H OCF₃ H H H S C₂H₄OCH₃ 157 H OCF₃ H H HS C₂H₄OC₂H₅ 158 H SCH₃ H H H S C₂H₄Ophenyl 159² H H H Cl H S C₂H₄Ophenyl160 H Cl H H H S C₂H₄SCH₃ 161⁴ H CH(CH₃)₂ H H F S2-(4-fluorophenoxy)ethyl 162 H OCF₃ H H H S C(═O)CH₃ 163⁹ H SCH₃ H H H SC(═O)CH₃ 164 H OCF₃ H H H S CO₂CH₃ 165 H OCF₃ H H H S CH₂CO₂C₂H₅ 166 HOCF₃ H H H S C₃H₆CO₂C₂H₅ 167⁴ H OCH₃ H H H S C₃H₆CO₂C₄H₉ 168 H CH(CH₃)₂H H F S 3-(4-fluorophenylcarbonyl)propyl 169⁴ H CH(CH₃)₂ H H F S3-(4-fluorophenylcarbonyl)propyl 170 H SCH₃ H H H S phenylmethyl 171² HCl H H F S 4-fluorophenylmethyl 172 H SCH₃ H H H S pyrid-4-yl 173 H SCH₃H H H S pyrid-4-ylmethyl where X is —CR¹¹R¹²CR¹³R¹⁴—; Y is —S—, whereR¹, R³ through R⁸, inclusively, and R¹² through R¹⁴, inclusively, arehydrogen; and

where v is 0; p is 0 and R^(c) is hydrogen: Cmpd. No R² R⁴³ R⁴⁴ 174 H HCH₃ 175 H CH₃ CH₃ 176 SCH₃ CH₃ CH₃ 177 CF₃ CH₃ CH₃ 178 OCF₃ CH₃ CH₃ 179—C₅H₁₀— where X is —CR¹¹R¹²CR¹³R¹⁴—; where R¹, R³ through R⁸,inclusively, and R¹² through R¹⁴, inclusively, are hydrogen; and

where v is 0; q is 0 and R^(d) is hydrogen; and u is 0: Cmpd. No Y R²R⁴⁵ 180 S H H 181 S H CH₃ 182 S H C₂H₅ 183 S SCH₃ CH₃ 184 S CF₃ CH₃ 185S OCF₃ CH₃ 186 O OCF₃ CH₃ where X is —CR¹⁸R¹⁹NR²⁰—, where R¹⁹ and R²⁰are hydrogen; Cmpd. No. R¹ Through R⁸, Inclusively Y R¹⁸ 187 H SCH₂NHCH₃ where X is —CR²¹═N—; Cmpd. R³ Through R⁸, No. R¹ R² InclusivelyY R²¹ 188 H Cl H S 1-methylpyrrolidin-3-yloxy where X is —CR²¹═N—; whereR⁴ through R⁸, inclusively, R¹², R¹³, and R¹⁴ are hydrogen; and

where v is 0; r is 0 and R^(e) is hydrogen; and u is 0: Cmpd. No. R² R³Y R⁴⁹ 189 Cl H S CH₃ 190 Cl H S(O) CH₃ 191 Cl H S CH₂CH═CH₂ 192 H Cl SCH₃ 193 CH(CH₃)₂ H S CH₃ 194 OCF₃ H S CH₃ where X is —NR¹⁷— and Y is—CR²⁴R²⁵CR²⁶R²⁷—; where R¹, R³ through R⁷, inclusively, and R²⁴ throughR²⁵, inclusively, are hydrogen; v is 0; and u is 0: Cmpd. No. R² R⁸ R¹⁷R⁴⁶ 195 H Cl C₃H₆N(CH₃)₂ — 196 H H

CH₃ 197 F H

CH₃ 198 OCH₃ H

CH₃ 199 SCH₃ H

CH₃ 200 CF₃ H

CH₃ 201 OCF₃ H

CH₃ where X is —NR¹⁷; and R¹, and R³ through R⁸, inclusively, arehydrogen: Cmpd. No. Y R³⁰ R² R¹⁷ R⁴⁷ R⁴⁸ 202 S — H C₃H₆NR⁴⁷R⁴⁸ H CH₃203² S — Cl C₃H₆NR⁴⁷R⁴⁸ H CH(CH₃)CH₂Ph 204⁶ S — Cl C₃H₆NR⁴⁷R⁴⁸ CH₃ CH₃205 S — OCH3 C₃H₆NR⁴⁷R⁴⁸ CH₃ CH₃ 206² S — C(O)CH₃ C₃H₆NR⁴⁷R⁴⁸ CH₃ CH₃207⁷ S — CF₃ C₃H₆NR⁴⁷R⁴⁸ —C₂H₄N(CH₃)C₂H₄— 208⁷ S — CF₃ C₃H₆NR⁴⁷R⁴⁸—C₂H₄N(C₂H₄OH)C₂H₄— 209 O — H C₃H₆NR⁴⁷R⁴⁸ H CH₃ 210 O — H C₃H₆NR⁴⁷R⁴⁸ HC₃H₇ 211 O — Cl C₃H₆NR⁴⁷R⁴⁸ H CH₃ 212 O — H C₃H₆NR⁴⁷R⁴⁸ CH₃ CH₃ 213 NR³⁰CH₃ H C₃H₆NR⁴⁷R⁴⁸ CH₃ CH₃ 214 NR³⁰ C₂H₅ H C₃H₆NR⁴⁷R⁴⁸ —C₅H₁₀— where X is—CR¹¹R¹²CR¹³R¹⁴—; where R¹, R³ through R⁸, inclusively, R¹³, and R¹⁴ arehydrogen, v is 0; m is 0 and R^(b) is hydrogen; and u is 0: Cmpd. No. R²R¹¹ R¹² Y R⁴² 215

OH S — 216 OCF₃

F S CH₃¹methanesulfonate salt;²maleate salt;³dimethanesulfonate salt;⁴dimaleate salt;⁵oxalate salt;⁶hydrochloride salt;⁷dihydrochloride salt;⁸disulfite salt;⁹sulfate salt;¹⁰oxalate salt-bis complex

The compounds of formula I useful in the present invention were testedfor insecticidal activity by observing mortality in a population ofcotton aphid (Aphis gossypii) on treated cotton plants caused by a testcompound, when compared to like populations of cotton aphid on untreatedplants. These tests were conducted in the following manner:

For each rate of application of test compound, two seven-to-ten days oldcotton seedlings (Gossypium hirsutium) grown in 7.6 cm diameter potswere selected for the test. Each test plant was infested with about 120adult cotton aphids by placing onto each test plant cuttings of leavesfrom cotton plants grown in a cotton aphid colony. Once infested, thetest plants were maintained for up to about 12 hours to allow completetranslocation of the aphids onto the test plant. A solution comprising1000 part per million (ppm) of each test compound was prepared bydissolving 10 milligrams of the test compound in 1 mL of acetone. Eachsolution was then diluted with 9 mL of a solution of 0.03 mL ofpolyoxyethylene(10) isooctylphenyl ether in 100 mL of water. About 2.5mL of solution of each test compound was needed to spray each replicateof test plant (5 mL total for each test compound). If needed, thesolution of 1000 ppm of test compound was serially diluted with asolution of 10% acetone and 300 ppm of polyoxyethylene(10)isooctylphenyl ether in water to provide solutions of each test compoundfor lower rates of application, for example, 300 ppm, 100 ppm, 30 ppm,or 10 ppm. Each replicate of test plant was sprayed with the solutionsof test compound until run-off on both the upper and lower surfaces ofthe leaves. All the test plants were sprayed using a DeVilbus AtomizerModel 152 (Sunrise Medical, Carlsbad, Calif.) at a pressure of about0.63-0.74 kilogram per square centimeter from a distance of about 30.5centimeters from the test plants. For comparison purposes, a solution ofa standard, such as amitraz or demethylchlordimeform (DCDM), prepared ina manner analogous to that set forth above, as well as a solution of 10%acetone and 300 ppm of polyoxyethylene(10) isooctylphenyl ether in watercontaining no test compound were also sprayed onto test plants. Uponcompletion of spraying the solutions of test compound, the solution ofstandard, and the solution containing no test compound, the plants wereallowed to dry. Upon completion of drying, the test plants were placedin a tray containing about 2.5 centimeters of water, where they weremaintained in a growth chamber for 24 hours. After this time, each plantwas assessed for percent mortality caused by the test compound whencompared to the population of aphids that was infested onto the testplants prior to treatment with test compound. A test compound wasdesignated as possessing insecticidal activity (SA) if there was 20% to75% mortality of cotton aphid on plants sprayed with that compound. Ifthere was 75% mortality or greater of the cotton aphid, a test compoundwas designated as being more insecticidally active (A). If there was 20%mortality or less of the cotton aphid, the test compound was termed asinactive (I).

Insecticidal activity data at selected rates of application from thistest are provided in Table 2. The test compounds of formula I areidentified by numbers that correspond to those in Table 1. TABLE 2Insecticidal Activity of Certain Tricyclic Derivatives Mortality ofCotton Aphid On Cotton Plants Compound 20% to 75% More Than 75% No.Mortality (SA) Mortality (A)  1 X  2 X  3 X  7 X  8** X  9 X  11 X  12 X 13 X  14 X  15 X  16 X  20 X  24 X  26 X  36 X  52 X  53 X  54 X  55 X 56 X  57 X  59 X  60 X  61 X  62 X  63 X  64** X  65** X  66* X  67** X 68 X  69* X  70* X  71 X  72** X  73** X  74** X  75** X  76 X  77** X 78** X  79** X  80** X  81** X  82** X  83** X  84** X  85** X  86 X 87 X  88** X  89** X  90 X  91 X  92 X  94** X  95 X  96** X  97** X 98** X  99** X 100** X 101** X 102** X 103** X 104** X 105** X 106** X107** X 108** X 109** X 110** X 111** X 112** X 113** X 114 X 115** X116 X 117 X 118** X 119** X 120 X 121 X 122** X 123** X 124** X 125** X126** X 127** X 128** X 129 X 131 138** X 139** X 140** X 141 X 142 X143 X 144** X 145** X 146** X 147 X 148 X 149** X 150** X 151 X 152** X153** X 154** X 155** X 156 X 157** X 158** X 159 X 160** X 161** X 162X 163** X 164 X 165 X 166** X 167** X 168** X 169** X 170 X 171** X 172X 173** X 178 X 183** X 185** X 186** X 187** X 188 X 189 X 190 X 191 X192 X 193 X 194 X 203** X 204** X 205** X 206**² X 207** X 208** X 217 XRate of application 1000 ppm*Rate of application 300 ppm**Rate of application 100 ppm

As set forth in Table 2, most all the compounds of formula I testedprovided 75% mortality or more of cotton aphid.

In a test conducted in the same manner as set forth above, certaincompounds of formula I were tested to determine a more definitivepercent mortality of cotton aphid. Insecticidal activity data atselected rates of application and insect exposure times from this testare provided in Table 3. TABLE 3 Insecticidal Activity of CertainTricyclic Derivatives Rate of Percent Mortality of Aphid CompoundApplication Cotton Aphid on Exposure to Test No. (ppm) Cotton PlantsCompound (Hours) 2 100 ppm    80% 96 hours 3 100 80 96 8 100 88 96 9 10026 72 11 100 42 96 12 100 26 72 15 100 28 96 20 100 37 72 26 100 84 7252 300 100  72 64 100 74 168 65 100 100  168 66 100 61 168 67 100 75 16869 100 69 168 70 100 57 168 71 100 100  168 72 100 100  168 73 100 35168 75 100 86 168 76 100 32 168 77 100 37 168 78 100 53 168 79 100 35168 80 1000 83 168 82 100 98 168 83 100 41 168 85 1000 92 168 87 1000 97168 88 100 35 168 89 100 55 168 90 1000 74 168 92 100 48 72 94 1000 100 72 95 1000 82 72 96 300 100  168 97 100 65 72 98 100 90 168 99 1000 100 168 100 1000 82 96 101 100 60 72 102 100 33 72 103 1000 90 72 104 100 75168 105 1000 85 96 106 1000 100  96 107 100 82 168 108 1000 100  168 1091000 100  168 110 300 65 168 111 100 94 72 112 100 92 72 113 100 78 72115 100 93 72 118 100 85 72 119 100 85 72 121 1000 65 72 122 100 88 72123 100 96 72 124 100 95 72 125 100 90 72 126 100 100  168 127 1000 100 168 128 100 95 72 131 100 90 168 138 1000 100  168 139 100 96 168 1401000 73 168 144 100 100  168 145 100 98 144 146 300 88 72 149 100 68 168150 100 93 72 151 300 72 72 152 300 74 168 153 300 93 168 154 100 83 72155 100 73 72 156 100 55 168 157 100 64 144 158 300 82 72 159 100 28 72160 100 71 72 161 100 73 72 162 300 31 168 163 1000 96 168 166 100 78144 167 300 66 168 168 100 77 72 169 100 71 72 171 100 85 72 173 1000 8296 183 1000 100  168 185 1000 100  168 186 100 100  168 187 100 94 168189 1000 55 168 194 100 51 168 205 500 40 72 207 1000 25 72 208 500 4372

As set forth in Table 3, compounds of formula I tested in this test, 60%of the compounds provided 75% or greater mortality of cotton aphid,while the remaining compounds of formula I, provided 26% to 74% controlof cotton aphid.

While this invention has been described with an emphasis upon preferredembodiments, it will be understood by those of ordinary skill in the artthat variations of the preferred embodiments may be used and that it isintended that the invention may be practiced otherwise than asspecifically described herein. Accordingly, this invention includes allmodifications encompassed within the spirit and scope of the inventionas defined by the following claims.

1. An insecticidal composition comprising at least one of aninsecticidally effective amount of a compound of formula I and at leastone insecticidally compatible carrier therefor, wherein the compound offormula I is:

wherein R¹ through R⁸, inclusively, are independently selected fromhydrogen, halogen, alkyl, cycloalkyl, alkenyl, alkynyl,trialkylsilylalkynyl, alkoxy, haloalkyl, haloalkoxy, alkylthio,alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl,haloalkylsulfonyl, dialkylaminosulfonyl, nitro, cyano, amino, formyl, oralkylcarbonyl; X is selected from —CR⁹R¹⁰—, —CR¹¹R¹²CR¹³R¹⁴—,—CR¹⁵═CR¹⁶—, NR¹⁷—, —CR¹⁸R¹⁹NR²⁰—, or C²¹═N—; and Y is selected from—CR²²R²³—, —CR²⁴R²⁵CR²⁶R²⁷, CR²⁸CR²⁹—, N³⁰—, —CR³¹R³²NR³³—, —O—, —S—,—S(O)—, —S(O)₂—, —CR³⁴R³⁵O—, —CR³⁶R³⁷S—, or —CR³⁸═N—; where R⁹ and R¹⁰are independently selected from hydrogen, alkyl, or(piperidin-4-yl)alkyl; or R⁹ and R¹⁰ may be taken together with

or with ═CHC₂H₄NR⁴⁰R⁴¹, where R³⁹, R⁴⁰ and R⁴¹ are independentlyselected from hydrogen; alkyl; hydroxylalkyl; alkoxyalkyl;alkylthioalkyl; alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl;aryloxyalkyl; arylcarbonylalkyl; arylcarbonyloxyalkyl, wherein aryl isoptionally substituted with one or more halogen, alkoxy, haloalkyl, oraryl; or R⁴⁰ and R⁴¹ may be taken together with —C₂H₄N(CH₃)C₂H₄— to forma piperazine ring; u is 0 or 1, and when u is 1, an N-oxide is formed; nis 0, and R^(a) is hydrogen; or n is 1 to 8, and R^(a) is selected fromone or more of alkyl, alkoxyalkyl, alkoxycarbonyl, and aryl, whereinaryl is optionally substituted with one or more halogen, alkoxy,haloalkyl, or aryl; R¹¹ is selected from hydrogen, alkyl,alkylaminoalkoxy, dialkylaminoalkoxy, N(alkyl)(alkylaminoalkyl),N(alkyl)(dialkylaminoalkyl), alkylaminoalkylalkynyl,dialkylaminoalkylalkynyl, morpholinyl, imidazolinyl,alkylpyrrolidinyloxy,

where v is 0 or 1, and when v is 1, A is a bridging group selected from—O—, —S—, —NH—, and —CH₂—; u is as described above; R⁴² through R⁴⁵,inclusively, are independently selected from hydrogen; alkyl; alkenyl;alkynyl; hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl;alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl; heteroarylalkyl;heteroarylalkylamino; wherein aryl and heteroaryl are optionallysubstituted with one or more halogen, alkoxy, haloalkyl, or aryl; or R⁴³and R⁴⁴ may be taken together with —C₅H₁₀— to form a piperidine ring; m,p, and q are 0, and R^(b), R^(c) and R^(d) are hydrogen; or m is 1 to 8,p is 1 to 7, and q is 1 to 10, and R^(b), R^(c), and R^(d),respectively, are independently selected from one or more of alkyl,alkoxyalkyl, alkylamino, dialkylamino, alkoxycarbonyl, or aryl, whereinaryl is optionally substituted with one or more halogen, alkoxy,haloalkyl, or aryl; or R¹¹ and R¹² may be taken together with

where R^(a), n, u, and R³⁹ are as described above; R², when not takentogether with R¹¹, and R¹³, R¹⁴, and R¹⁶, are independently selectedfrom hydrogen, hydroxy, halogen, alkyl, alkoxy, alkylcarbonyl,alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy, alkylaminocarbonyl,dialkylaminocarbonyl, alkylaminocarbonyloxy, dialkylaminocarbonyloxy,alkylaminosulfonyl, or dialkylaminosulfonyl; R¹⁵ is selected from

where m, u, v, A, R^(b) and R⁴² are as described above; R¹⁷ is hydrogen;alkyl; alkoxyalkyl; alkoxycarbonyl; dialkylaminoalkyl;alkylaminocarbonyl; dialkylaminocarbonyl; alkylsulfonyl; aryl, andarylalkyl wherein aryl is optionally substituted with one or morehalogen, alkoxy, haloalkyl, or aryl;

or —C₃H₆NR⁴⁷R⁴⁸ where A, v, and u are as described above; R⁴⁶ isselected from selected from hydrogen; alkyl; alkenyl; alkynyl;hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl;alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl; heteroarylalkyl;heteroarylalkylamino; wherein aryl and heteroaryl are optionallysubstituted with one or more halogen, alkoxy, haloalkyl, or aryl; R⁴⁷and R⁴⁸ are independently selected from hydrogen and alkyl; or R⁴⁷ andR⁴⁸ may be taken together with —C₅H₁₀— to form a piperidine ring, orwith —C₂H₄N(CH₃)C₂H₁—, or —C₂H(C₂H₄OH)C₂H₄— to form a piperazine ring;R¹⁸ and R¹⁹ are independently selected from hydrogen, alkyl, amino,alkylaminoalkyl, and dialkylaminoalkyl; R²⁰ is selected from hydrogen;alkyl; alkoxyalkyl; alkoxycarbonyl; dialkylaminoalkyl;alkylaminocarbonyl; dialkylaminocarbonyl; alkylsulfonyl; aryl, andarylalkyl wherein aryl is optionally substituted with one or morehalogen, alkoxy, haloalkyl, or aryl; R²¹ is selected from hydrogen,alkyl,

where A, v, and u are as described above; R⁴⁹ through R⁵², inclusively,are independently selected from hydrogen; alkyl; alkenyl, alkynyl,hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl,alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;arylcarbonylalkyl; arylcarbonyloxyalkyl, heteroaryl, heteroarylalkyl,heteroarylalkylamino, wherein aryl and heteroaryl are optionallysubstituted with one or more halogen, alkoxy, haloalkyl, or aryl; or R⁵⁰and R⁵¹ may be taken together with —C₅H₁₀— to form a piperidine ring; r,s, and t are 0, and R^(e), R^(f), and R^(g) are hydrogen, or r is 1 to8, s is 1 to 7, t is 1 to 10, and R^(e), R^(f), and R^(g), respectively,are independently selected from one or more of alkyl, alkoxyalkyl,alkylamino, dialkylamino, alkoxycarbonyl, or aryl, wherein aryl isoptionally substituted with one or more halogen, alkoxy, haloalkyl, oraryl; R²² through R²⁹, inclusively, are independently selected fromhydrogen, and alkyl; R³⁰ is selected from hydrogen; alkyl; alkoxyalkyl;alkoxycarbonyl; dialkylaminoalkyl; alkylaminocarbonyl;dialkylaminocarbonyl; alkylsulfonyl; aryl, and arylalkyl wherein aryl isoptionally substituted with one or more halogen, alkoxy, haloalkyl, oraryl; R³¹ and R³² are independently selected from hydrogen, and alkyl,R³³ is selected from hydrogen; alkyl; alkoxyalkyl; alkoxycarbonyl;dialkylaminoalkyl; alkylaminocarbonyl; dialkylaminocarbonyl;alkylsulfonyl; aryl, and arylalkyl wherein aryl is optionallysubstituted with one or more halogen, alkoxy, haloalkyl, or aryl; R³⁴through R³⁸, inclusively, are independently selected from hydrogen, andalkyl; and, agriculturally acceptable salts thereof.
 2. An insecticidalcomposition of claim 1, wherein X is —CR⁹R¹⁰— and Y is selected from—O—, —S—, —CR²²R²³—, and —CR³⁴R³⁵O—; where R⁹ and R¹⁰ are taken togetherwith

where R³⁹ is selected from hydrogen; alkyl; hydroxylalkyl; alkoxyalkyl;alkylthioalkyl; alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl;aryloxyalkyl; arylcarbonylalkyl; arylcarbonyloxyalkyl, wherein aryl isoptionally substituted with one or more halogen, alkoxy, haloalkyl, oraryl; and, R²², R¹, R³⁴ and R³⁵ are independently selected from hydrogenand alkyl.
 3. An insecticidal composition of claim 1, wherein X is—CR¹¹R¹²CR¹³R¹⁴— and Y is selected from —O—, —S— and —CR²²R²³—; whereR¹¹ is selected from

where R⁴² and R⁴⁵ are independently selected from hydrogen; alkyl;alkenyl; alkynyl; hydroxylalkyl; alkoxyalkyl; alkylthioalkyl;alkylcarbonyl; alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl;aryloxyalkyl; arylcarbonylalkyl; arylcarbonyloxyalkyl; heteroaryl;heteroarylalkyl; heteroarylalkylamino; wherein aryl and heteroaryl areoptionally substituted with one or more halogen, alkoxy, haloalkyl, oraryl; R¹² is selected from selected from hydrogen, hydroxy, halogen,alkyl, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl,alkoxycarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl,alkylaminocarbonyloxy, dialkylaminocarbonyloxy, alkylaminosulfonyl, anddialkylaminosulfonyl; R¹³ and R¹⁴ are hydrogen; and, R²² and R²³ areindependently selected from hydrogen and alkyl.
 4. An insecticidalcomposition of claim 1, wherein X is —CR¹⁸R¹⁹NR²⁰— and Y is selectedfrom —O—, —S— and —CR²²R²³—; where R²⁰ is selected from hydrogen, alkyl,alkoxyalkyl, alkoxycarbonyl, dialkylaminoalkyl, alkylaminocarbonyl, anddialkylaminocarbonyl; and, R²² and R²³ are independently selected fromhydrogen and alkyl.
 5. An insecticidal composition of claim 1, wherein Xis —CR²¹═N— and Y is selected from —S— and —CR²²R²³—; where R²¹ is

where R⁴⁹ is selected from hydrogen; alkyl; alkenyl, alkynyl,hydroxylalkyl; alkoxyalkyl; alkylthioalkyl; alkylcarbonyl,alkoxycarbonylalkyl; haloalkoxycarbonyl; arylalkyl; aryloxyalkyl;arylcarbonylalkyl; arylcarbonyloxyalkyl, heteroaryl, heteroarylalkyl,heteroarylalkylamino, wherein aryl and heteroaryl are optionallysubstituted with one or more halogen, alkoxy, haloalkyl, or aryl; and,R²² and R²³ are independently selected from hydrogen and alkyl.
 6. Theinsecticidal composition of claim 1, further comprising one or moresecond compounds.
 7. The insecticidal composition of claim 2, furthercomprising one or more second compounds.
 8. The insecticidal compositionof claim 3, further comprising one or more second compounds.
 9. Theinsecticidal composition of claim 4, further comprising one or moresecond compounds.
 10. The insecticidal composition of claim 5, furthercomprising one or more second compounds.
 11. A method of controllinginsects, comprising applying an insecticidally effective amount of acomposition of claim 1 to a locus where insects are present or areexpected to be present.
 12. A method of controlling insects, comprisingapplying an insecticidally effective amount of a composition of claim 2to a locus where insects are present or are expected to be present. 13.A method of controlling insects, comprising applying an insecticidallyeffective amount of a composition of claim 3 to a locus where insectsare present or are expected to be present.
 14. A method of controllinginsects, comprising applying an insecticidally effective amount of acomposition of claim 4 to a locus where insects are present or areexpected to be present.
 15. A method of controlling insects, comprisingapplying an insecticidally effective amount of a composition of claim 5to a locus where insects are present or are expected to be present. 16.A method of controlling insects, comprising applying an insecticidallyeffective amount of a composition of claim 6 to a locus where insectsare present or are expected to be present.
 17. A method of controllinginsects, comprising applying an insecticidally effective amount of acomposition of claim 7 to a locus where insects are present or areexpected to be present.
 18. A method of controlling insects, comprisingapplying an insecticidally effective amount of a composition of claim 8to a locus where insects are present or are expected to be present. 19.A method of controlling insects, comprising applying all insecticidallyeffective amount of a composition of claim 9 to a locus where insectsare present or are expected to be present.
 20. A method of controllinginsects, comprising applying an insecticidally effective amount of acomposition of claim 10 to a locus where insects are present or areexpected to be present.